Halogenated and nitro halogenated thiophenes as agricultural fungicides



l 'atented June 10, 1952 HALOGENATED AND NITRO HALOGENATED THIOPHENES AS AGRICULTURAL FUNGI- cross Kenneth G. Nolan, South Nor-walk, and John H.

Fletcher, Riverside, Conn., assignors to American Cyanamid Company, New York, N. Y., a

corporation of Maine No Drawing. Application May 7, 1947, Serial No. 746,626

1 Claim.

1 The present invention relates to fungicides and more particularly to methods and compositions for the control of fungus organisms which attack organic materials. It has been discovered that the thiophene'compounds which conform to the general formula wherein X stands for a member of the group consisting of hydrogen, nitro, and halogen and combinations thereof, and n is an integer of from 1 to 3, possess high fungicidal power and are particularly effective in protecting seeds and seedlings from seed-borne and soil-borne organisms which cause seed rot, seedling blight and damping-off.

As showing the wide diversity of compounds which may be used for the purposes of this invention, the following may be mentioned: 2- chlorothiophene, 2,5-dichlorothiophene, 2,3,5-trichlorothiophene, tetrachlorothiophene, B-bromothiophene, 2,4-dibromothiophene, 2,3,4-tribromothiophene, tetrabromothiophene, 2 iodothiophene, 2,5-diiodothiophene, 2,3-diiodothiophene, 2,3,5 triiodothiophene, chloro-2,3,4-tribromothiophene, 3-chloro-2,4,5-triiodothiophene, 2,3- dicholor-4,5-dibromothiophene, 2,3-dichloro-4,5-e diiodothiophene, 2,5 dichloro 3,4-dibromothiophene, 3,4-dichloro-2,5-dibromothiophene, 2,3,4- trichloro-5-bromothiophene, 2,3,5 trichloro 4 iodothiophene, 3-bromo-2,5-diiodothiophene, 2,3- dibromo-5-iodothiophene, 2,5-dibromo 3,4 diiodothiophene, 3,4 dibromo 2 iodothiophene, 2,3,5 tribromo-4-iodothiophene, 4,5-dichloro-2- nitrothiophene, 3,4,5-trichloro-2-nitrothiophene, 2,3,5 trichloro-4-nitrothiophene, 3-bromo-2-n1- trothiophene, 3,5 dibromo 2 nitrothiophene, 2,4,5-tribromo-3-nitrothiophene, 5-iodo-2-nitrothiophene, 4,5-diiodo-2-nitrothiophene, 2,5-dichloro-3,4-dinitrothiophene, 3,4-dibromo-2,5-dinitrothiophene, 2,5 dibromo 3,4 dinitrothiophene, and 3,4-diiodo-2,5-dinitrothiophene.

The more volatile members of the above series of thiophenes may be employed as soil fumigants for preventing or arresting infestations of fungi, molds, and similar noxious organisms. The relatively non-volatile members are eminently suited halogen- X,-

for protecting seeds from fungus attack. Mix- 2 tures of the thiophenes are particularlysuited for seed treatment in controlling a complex of both seed-borne and soil-borne organisms.

The thiophene compounds of the present invention may also be used for the protection of plants against fungus organisms which cause defoliation, leaf blight, mildew, fruit rot and. the like.

Corn seeds infected with Diplodia zeae were treated with dusts consisting of equal parts of representative thiophene compounds as listed below and tale in the proportion of 2 oz. of dust per bushel of corn. The treated seeds were placed between moist blotters in a germination cabinet for a period of 7 days, the temperature of the cabinet being maintained at about C. Excellent control of the root rot organism was obtained with either tetrabromothiophene, 2,5-dichloro- 3,4-dinitrothiophene, or 2,3,5-tribromo-4-nitrothiophene. Saprophytic fungi, such as the Penicillium, Aspergillus and Rhizopus species present on the corn seed, were also controlled by such compounds as 2,5-dibromo-3,4-dinitrothiophene, 2,5 dichloro 3,4 dinitrothiophene and 2,5 dichloro-3-bromo-4-nitrothiophene.

Barley seeds infected with Gibberella and Helmintho'sporium, organisms causing seedling blight of small grains, were treated with dusts containing the thiophenes in the proportion of 2 oz. of dust per bushel of seed. The treated seeds were planted in field plots with approximately 250 seeds per plot, using four replications per treatment. Table 1 gives the total number of seedlings which emerged from each treatment.

Wheat seeds heavily infected with: Heliumthosporium were treated with dusts containing the thiophenes in the proportion of 2 oz. of dust per bushel of seed. The treated seeds were planted in field plots with approximately 250 seeds per plot, using four replications per treatment. Table 2 gives the total number of seedlings which emerged from each treatment.

Table 2 Per- Wheat Dust cent Seedlings 1. None (untreated seed) 242 2. 2,5-dichlor-3,-i-dinitrothiophene 25 396 talc 75 3. 2,5-dichioro-3,4-dibromothiophene 4 0 2,fi-dichloro-3,4-dinitrothiophene. c 4. 2,5-dichloro-3,4-dinitrothiophene.

let-rabromothiophene a 5. 2,5-dichloro-3A-dinitrothiophene 2,31,5-tribromo-4-nitrothiophen ta c Corn seeds were treated with dusts containing the thiophenes in the proportion of oz. of "dust per bushel ofseed. The treated seeds were plantedin field plots with approximately 100 seeds per plot, using four replications'per treatment. "The soil was known to be'infested with a "numberof fungus organisms including Pythium species. Table 3 gives the per cent emergence or stand of seedlings from each" treatment.

Pea' seeds (variety Perfection) were treated with-dusts containing the thiophenes in the proportion of one part of dust per 500 parts of seed r- -on a weight basis. The treated seeds were planted in Pythium infested soil in plots with ten seeds "per fplot, using five replications per' treatment.

Tabled-gives the per cent emergence or stand '--of*seedlings from each treatment, counts bein made fourteen days after planting.

" Table 4 P Per cent er emergence Dust -cent e oipea seedlings 1. None (untreated seed) 00.0 2. af1)-dichloro-3,4-dinitrothiophen 80 0 c 3. tetrabromothiophene v 2,51-dichloro-3,4-dinitrothiophene. 1 84.0.

' ta 0 4. 2,5-dichloro-3,4-dinitrothiophene. 25

2,3?5-tribromo4-nitrothiopliens 92.0 tee r ii'l ho abflity' tamer-mistressescorprotectiseeds from fungus attack is further demonstrated by' the data given in Table 4. No germination of the non-dusted pea. seed occurred, whereas from 80 to 92% of the treated seeds germinated and developed into plants.

Seeds of other plants which may be advantageously protected from attack by fungus diseases in accordance with this invention include oats.

. rye, cotton, beets, tomatoes and beans.

In addition to being highly efiicacious against seed-borne and soil-borne organisms, the thiophones of the present invention may be employed for many purposes of preserving and disinfecting,

for example, the preservation of wood, the prevention' of mildew formation, the preservation of glue, the preservation of paints and the prevention offungus attack on cloth, rubber, leather,

' rope paper, resins, and the like, using those normally liquidsas' such and others in solution or suspension, and those normally solids as such.

Although the above thiophenes may be used alone as fungicides, it is usually preferable to mix them with, or adsorb or absorb them on an inert carrier or a spreading material such as talc, bentonite, fullers earth, pumice, silica, silicates, chalk, wood flour and the like. The thiophenes may also be used admixed with carriers that are active of themselves, for example, other fungicides, insecticides, germicides, hormones and fertilizers. The proportion of the thiophene tothe carrier may be from 1 to 95% or may be varied in accordance with the particular efiects desired and the conditions under which it is to be used. Under some circumstances, it may be desirable to apply the thiophene compound in the form of a solution or suspension inwater or other liquid, and the present invention does not preclude such use.

Other substituted thiophenes which may be similarly'employed for the control of fungus organisms include 2-methylthiophene, 3-methylthiophene, 2-isopropylthiophene, Z-methyl-B- ethylthiophene, 2,3,4-trimethylthiophene, '2,5-di- 45- ethylthiophene, 2,3,5-trimethyl-4-ethylthiophene,

2-ethy1-5-is0amylthi0phene, 2-methy1-5-n-octy1- thiophene, 2-benzlythiophene, 2,5-dibenzylthio- 'phene, 2 methyl --3,4,5 triiodothiophene, 2 methyl 3,5 dibromothiophene, 2 acetylthiophene, 2 benzoylthiophene, 2 aeetyl --5 iodothiophene, 2 acetyl 4,5 dibromothiophene, 2 acetyl 3,4,5 trichlorothiophene, 2 acetyl 3 methyl 4,5 dibromothiophene,Z-benzoyl 1 3,4 dibromothiophene, 2 benzoyl 4,5 diiodothiophene and the like.

While the invention has sheen-described with particular reference to specific embodiments, it

is to be understood that it is not to be limited thereto but is to be construed broadly and restriated solely by the scope of the appended claim.

W e claim A fungicidal composition 1 comprising: a titlephene coinpound-of the general formulawherein Y stands for halogen, Xstands for, nitro,

m isan integer of from 1 to 3, n is-anv integer of from I to.2, the sum m+n-being an integer of from'2 to 4, and a carrier dust therefor.

. :KENNETH' G; NOLAN. JOHN H.i FLETCHER.

ititeferences onfollowinmmfl) 5 6 REFERENCES CITED OTHER REFERENCES The following references are of record in the Richter, Organic Chemistry, volume III, P. file of this patent: Blakistons Son and Co. Philadelphia 1923, pages UNITED STATES PATENTS 21 to 5 Alles J. Pharm. and Exp. Ther., volume 72,

Number Name Date 1941 page 2 5 fii ig -ylyg The Dispensatory of the U. 5., 22nd edition, I J. P. L' no t C. Ph'l 1h 1937, es 2,100,493 Smith et a1. Nov. 30, 1937 mm o t 1 me p pag 2393325 Morns 1946 10 Oil, Paint and Drug Reporter, Apri1 12, 1943,

FOREIGN PATENTS page 46. Number Country Date 347,451 Great Britain Apr. 30, 1931 81 ,749 France May 15, 1937 15 

